Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103026064/bm1551sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103026064/bm1551Isup2.hkl |
CCDC reference: 231029
Addition of bpea·0.5H2O (0.23 g, 1.0 mmol) (Leaver et al., 2003) to a solution of CuCl2·2H2O (0.18 g, 1.0 mmol) in MeOH (30 ml) afforded a deep-blue solution. Slow evaporation from this solution gave dark-blue plates of (I) that were filtered off, washed with water and dried in vacuo (yield 0.25 g, 73%). The dried material contains a reduced water content compared with the freshly prepared single crystals, analysing as the monohydrate of the complex. Analysis found: C 47.6, H 5.6, N 11.2%; calculated for [C28H36Cu2N6O2]Cl2·H2O: C 47.7, H 5.4, N 11.9%.
The asymmetric unit contains half a dimeric complex dication lying across a crystallographic inversion centre, one Cl− anion, two wholly occupied water molecules (O21 and O22), and a disordered region comprising three O atoms (O23A—O23C) with refined occupancies of 0.40 (O23A), 0.35 (O23B) and 0.25 (O23C). All non-H atoms, except for the three disordered O atoms, were refined anisotropically. All C-bound H atoms were placed in calculated positions and refined using a riding model. The fixed C—H distances were C—H(aryl) = 0.95 and C—H(alkyl) = 0.99 Å, with all Uiso(H) = 1.2Ueq(C). The H atoms bound to atoms O2, N3 and O22, and one of the H atoms bound to O21 (see Comment), were located in the difference map and allowed to refine freely with a common displacement parameter, and (for atoms H2, H21A, H22A and H22B) subject to a restrained O—H distance of 0.77 (2) Å; no N3—H3 restraint was applied. H atoms associated with the disordered O atoms O23A—O23C were not located.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: local program.
[Cu2(OH)2(C14H17N3)2]Cl2·6H2O | Z = 1 |
Mr = 794.70 | F(000) = 414 |
Triclinic, P1 | Dx = 1.491 Mg m−3 |
a = 9.2875 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.9802 (2) Å | Cell parameters from 17493 reflections |
c = 10.9261 (2) Å | θ = 2.9–27.5° |
α = 63.4321 (8)° | µ = 1.41 mm−1 |
β = 82.2565 (7)° | T = 150 K |
γ = 77.9460 (8)° | Plate, dark blue |
V = 884.85 (3) Å3 | 0.36 × 0.21 × 0.07 mm |
Nonius KappaCCD area-detector diffractometer | 4033 independent reflections |
Radiation source: fine-focus sealed tube | 3781 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −12→12 |
Tmin = 0.631, Tmax = 0.908 | l = −14→14 |
17493 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0426P)2 + 0.5339P] where P = (Fo2 + 2Fc2)/3 |
4033 reflections | (Δ/σ)max = 0.001 |
228 parameters | Δρmax = 0.46 e Å−3 |
4 restraints | Δρmin = −0.71 e Å−3 |
[Cu2(OH)2(C14H17N3)2]Cl2·6H2O | γ = 77.9460 (8)° |
Mr = 794.70 | V = 884.85 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.2875 (2) Å | Mo Kα radiation |
b = 9.9802 (2) Å | µ = 1.41 mm−1 |
c = 10.9261 (2) Å | T = 150 K |
α = 63.4321 (8)° | 0.36 × 0.21 × 0.07 mm |
β = 82.2565 (7)° |
Nonius KappaCCD area-detector diffractometer | 4033 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 3781 reflections with I > 2σ(I) |
Tmin = 0.631, Tmax = 0.908 | Rint = 0.054 |
17493 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 4 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.46 e Å−3 |
4033 reflections | Δρmin = −0.71 e Å−3 |
228 parameters |
Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. The asymmetric unit contains half a dimeric complex dication lying across a crystallographic inversion centre; one chloride anion; two wholly occupied water molecules (O21 and O22); and a disordered region comprising three oxygen atoms (O23A—O23C) with refined occupancies of 0.40 (O23A), 0.35 (O23B) and 0.25 (O23C). All non-H atoms except for the three disordered O atoms were refined anisotropically. All C-bound H atoms were placed in calculated positions and refined using a riding model. The H atoms bound to O2, N3, O21 (see below) and O22 were located in the difference map and allowed to refine freely with a common thermal parameter, and (for H2, H21A, H22A and H22B) subject to a restrained O—H distance of 0.77 (2) Å; no N3—H3 restraint was applied. H atoms associated with the disordered O atoms O23A—O23C were not located. Only one H atom bound to O21 (H21A) was located in the difference map. This water molecule probably forms a hydrogen-bonded pair with O21i (related by x, 1 − y, 1 − z), since O21···O21i = 2.831 (4) Å and H21A—O21···O21'i = 100 (4)°. If this is true, then the putative proton H21B must be disordered over at least two sites, being 50% occupied at a position lying near the O21···O21i vector. This would explain our inability to locate this H atom. The disordered solvent region is also apparently positioned so as to allow hydrogen bonding to O22, O21ii (related by 1 + x, y, z) and O23Aiii–O23Ciii (related by 2 − x, −y, 1 − z), since the relevant O···O distances all lie in the range 2.55–2.97 Å. Since one (or more) of O23A–O23C probably acts as a H-bond acceptor for at least one of the disorder orientations of H21B'', this at least partially explains the existence of disorder in this region of the lattice. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.55332 (2) | 0.59259 (2) | 0.05713 (2) | 0.02178 (9) | |
O2 | 0.39468 (15) | 0.47903 (15) | 0.08527 (14) | 0.0262 (3) | |
H2 | 0.368 (3) | 0.434 (3) | 0.158 (2) | 0.037 (3)* | |
N3 | 0.50709 (19) | 0.59021 (19) | 0.24496 (16) | 0.0262 (3) | |
H3 | 0.492 (3) | 0.508 (3) | 0.283 (3) | 0.037 (3)* | |
C4 | 0.6330 (2) | 0.5976 (3) | 0.3106 (2) | 0.0352 (5) | |
H4A | 0.6122 | 0.5571 | 0.4109 | 0.042* | |
H4B | 0.6456 | 0.7048 | 0.2759 | 0.042* | |
C5 | 0.7746 (2) | 0.5061 (3) | 0.2810 (2) | 0.0371 (5) | |
H5A | 0.8464 | 0.4817 | 0.3503 | 0.044* | |
H5B | 0.7532 | 0.4090 | 0.2897 | 0.044* | |
C6 | 0.8428 (2) | 0.5891 (2) | 0.1403 (2) | 0.0285 (4) | |
N7 | 0.75411 (17) | 0.65056 (17) | 0.03419 (16) | 0.0250 (3) | |
C8 | 0.8100 (2) | 0.7295 (2) | −0.0932 (2) | 0.0275 (4) | |
H8 | 0.7461 | 0.7751 | −0.1674 | 0.033* | |
C9 | 0.9563 (2) | 0.7464 (2) | −0.1199 (2) | 0.0320 (4) | |
H9 | 0.9926 | 0.8028 | −0.2106 | 0.038* | |
C10 | 1.0494 (2) | 0.6790 (2) | −0.0108 (2) | 0.0345 (4) | |
H10 | 1.1513 | 0.6861 | −0.0261 | 0.041* | |
C11 | 0.9915 (2) | 0.6017 (2) | 0.1198 (2) | 0.0330 (4) | |
H11 | 1.0530 | 0.5573 | 0.1957 | 0.040* | |
C12 | 0.3718 (2) | 0.6951 (2) | 0.2563 (2) | 0.0322 (4) | |
H12A | 0.3624 | 0.6900 | 0.3496 | 0.039* | |
H12B | 0.2848 | 0.6604 | 0.2439 | 0.039* | |
C13 | 0.3717 (3) | 0.8598 (2) | 0.1517 (2) | 0.0373 (5) | |
H13A | 0.3033 | 0.9268 | 0.1866 | 0.045* | |
H13B | 0.4717 | 0.8838 | 0.1436 | 0.045* | |
C14 | 0.3275 (2) | 0.8960 (2) | 0.0113 (2) | 0.0286 (4) | |
N15 | 0.41154 (17) | 0.82107 (17) | −0.05647 (16) | 0.0258 (3) | |
C16 | 0.3752 (2) | 0.8568 (2) | −0.18395 (19) | 0.0288 (4) | |
H16 | 0.4337 | 0.8036 | −0.2319 | 0.035* | |
C17 | 0.2575 (2) | 0.9665 (2) | −0.2491 (2) | 0.0319 (4) | |
H17 | 0.2375 | 0.9900 | −0.3402 | 0.038* | |
C18 | 0.1694 (2) | 1.0413 (2) | −0.1779 (2) | 0.0341 (4) | |
H18 | 0.0866 | 1.1160 | −0.2187 | 0.041* | |
C19 | 0.2045 (2) | 1.0052 (2) | −0.0472 (2) | 0.0328 (4) | |
H19 | 0.1450 | 1.0545 | 0.0035 | 0.039* | |
Cl20 | 0.36186 (7) | 0.27589 (6) | 0.41280 (5) | 0.04245 (15) | |
O21 | 0.0392 (2) | 0.3447 (2) | 0.5372 (2) | 0.0521 (4) | |
H21A | 0.109 (3) | 0.342 (3) | 0.497 (3) | 0.037 (3)* | |
O22 | 0.6393 (2) | 0.0506 (2) | 0.5830 (2) | 0.0512 (4) | |
H22A | 0.636 (3) | −0.027 (2) | 0.579 (3) | 0.037 (3)* | |
H22B | 0.569 (3) | 0.104 (3) | 0.538 (3) | 0.037 (3)* | |
O23A | 0.9213 (6) | 0.1261 (7) | 0.4943 (6) | 0.0522 (12)* | 0.40 |
O23B | 0.9119 (9) | 0.1179 (10) | 0.5613 (10) | 0.056 (2)* | 0.35 |
O23C | 0.9315 (12) | 0.0831 (13) | 0.5609 (13) | 0.050 (3)* | 0.25 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02181 (13) | 0.02336 (13) | 0.02222 (13) | −0.00487 (8) | −0.00280 (8) | −0.01072 (9) |
O2 | 0.0279 (7) | 0.0271 (7) | 0.0270 (7) | −0.0085 (5) | −0.0019 (5) | −0.0129 (6) |
N3 | 0.0317 (8) | 0.0245 (8) | 0.0234 (7) | −0.0085 (6) | −0.0021 (6) | −0.0095 (6) |
C4 | 0.0423 (11) | 0.0444 (12) | 0.0238 (9) | −0.0187 (9) | −0.0034 (8) | −0.0138 (8) |
C5 | 0.0372 (11) | 0.0382 (11) | 0.0312 (10) | −0.0100 (9) | −0.0144 (9) | −0.0058 (9) |
C6 | 0.0286 (9) | 0.0241 (9) | 0.0342 (10) | −0.0040 (7) | −0.0084 (8) | −0.0121 (8) |
N7 | 0.0244 (7) | 0.0237 (7) | 0.0289 (8) | −0.0044 (6) | −0.0047 (6) | −0.0119 (6) |
C8 | 0.0286 (9) | 0.0264 (9) | 0.0302 (9) | −0.0057 (7) | −0.0024 (7) | −0.0139 (8) |
C9 | 0.0298 (10) | 0.0302 (10) | 0.0413 (11) | −0.0093 (8) | 0.0051 (8) | −0.0201 (9) |
C10 | 0.0226 (9) | 0.0321 (10) | 0.0574 (13) | −0.0059 (7) | −0.0009 (9) | −0.0266 (10) |
C11 | 0.0269 (9) | 0.0286 (9) | 0.0473 (12) | −0.0015 (7) | −0.0124 (8) | −0.0181 (9) |
C12 | 0.0391 (11) | 0.0334 (10) | 0.0264 (9) | −0.0057 (8) | 0.0015 (8) | −0.0159 (8) |
C13 | 0.0545 (13) | 0.0285 (10) | 0.0341 (10) | −0.0033 (9) | −0.0069 (9) | −0.0182 (9) |
C14 | 0.0357 (10) | 0.0217 (8) | 0.0301 (9) | −0.0065 (7) | −0.0007 (8) | −0.0123 (7) |
N15 | 0.0266 (8) | 0.0231 (7) | 0.0272 (8) | −0.0045 (6) | −0.0014 (6) | −0.0102 (6) |
C16 | 0.0289 (9) | 0.0293 (9) | 0.0251 (9) | −0.0043 (7) | 0.0026 (7) | −0.0104 (7) |
C17 | 0.0340 (10) | 0.0301 (10) | 0.0259 (9) | −0.0042 (8) | −0.0037 (8) | −0.0069 (8) |
C18 | 0.0308 (10) | 0.0254 (9) | 0.0403 (11) | −0.0009 (7) | −0.0054 (8) | −0.0097 (8) |
C19 | 0.0351 (10) | 0.0247 (9) | 0.0396 (11) | −0.0019 (8) | 0.0000 (8) | −0.0166 (8) |
Cl20 | 0.0592 (4) | 0.0344 (3) | 0.0334 (3) | −0.0159 (2) | 0.0109 (2) | −0.0144 (2) |
O21 | 0.0444 (10) | 0.0494 (10) | 0.0612 (12) | 0.0043 (8) | −0.0136 (9) | −0.0250 (9) |
O22 | 0.0535 (11) | 0.0556 (12) | 0.0594 (12) | −0.0180 (9) | −0.0015 (9) | −0.0346 (10) |
Cu1—O2 | 1.9528 (13) | C10—C11 | 1.379 (3) |
Cu1—O2i | 1.9527 (14) | C10—H10 | 0.9500 |
Cu1—N3 | 2.0298 (16) | C11—H11 | 0.9500 |
Cu1—N7 | 2.0175 (16) | C12—C13 | 1.526 (3) |
Cu1—N15 | 2.2646 (16) | C12—H12A | 0.9900 |
Cu1—Cu1i | 3.0194 (4) | C12—H12B | 0.9900 |
O2—H2 | 0.75 (2) | C13—C14 | 1.505 (3) |
N3—C4 | 1.482 (3) | C13—H13A | 0.9900 |
N3—C12 | 1.488 (3) | C13—H13B | 0.9900 |
N3—H3 | 0.77 (3) | C14—N15 | 1.346 (2) |
C4—C5 | 1.522 (3) | C14—C19 | 1.398 (3) |
C4—H4A | 0.9900 | N15—C16 | 1.347 (3) |
C4—H4B | 0.9900 | C16—C17 | 1.383 (3) |
C5—C6 | 1.505 (3) | C16—H16 | 0.9500 |
C5—H5A | 0.9900 | C17—C18 | 1.387 (3) |
C5—H5B | 0.9900 | C17—H17 | 0.9500 |
C6—N7 | 1.345 (2) | C18—C19 | 1.375 (3) |
C6—C11 | 1.393 (3) | C18—H18 | 0.9500 |
N7—C8 | 1.350 (2) | C19—H19 | 0.9500 |
C8—C9 | 1.381 (3) | O21—H21A | 0.73 (2) |
C8—H8 | 0.9500 | O22—H22A | 0.80 (2) |
C9—C10 | 1.393 (3) | O22—H22B | 0.81 (2) |
C9—H9 | 0.9500 | ||
O2i—Cu1—O2 | 78.73 (6) | C8—C9—C10 | 118.45 (19) |
O2i—Cu1—N7 | 91.06 (6) | C8—C9—H9 | 120.8 |
O2—Cu1—N7 | 162.93 (6) | C10—C9—H9 | 120.8 |
O2i—Cu1—N3 | 160.57 (7) | C11—C10—C9 | 118.98 (18) |
O2—Cu1—N3 | 91.00 (6) | C11—C10—H10 | 120.5 |
N7—Cu1—N3 | 94.57 (7) | C9—C10—H10 | 120.5 |
O2i—Cu1—N15 | 101.78 (6) | C10—C11—C6 | 119.88 (19) |
O2—Cu1—N15 | 93.65 (6) | C10—C11—H11 | 120.1 |
N7—Cu1—N15 | 101.88 (6) | C6—C11—H11 | 120.1 |
N3—Cu1—N15 | 95.24 (6) | N3—C12—C13 | 113.32 (17) |
Cu1i—O2—Cu1 | 101.27 (6) | N3—C12—H12A | 108.9 |
Cu1i—O2—Cu1 | 101.27 (6) | C13—C12—H12A | 108.9 |
Cu1i—O2—H2 | 126 (2) | N3—C12—H12B | 108.9 |
Cu1—O2—H2 | 118 (2) | C13—C12—H12B | 108.9 |
C4—N3—C12 | 112.09 (16) | H12A—C12—H12B | 107.7 |
C4—N3—Cu1 | 115.55 (13) | C14—C13—C12 | 114.63 (17) |
C12—N3—Cu1 | 115.20 (12) | C14—C13—H13A | 108.6 |
C4—N3—H3 | 106 (2) | C12—C13—H13A | 108.6 |
C12—N3—H3 | 109 (2) | C14—C13—H13B | 108.6 |
Cu1—N3—H3 | 97 (2) | C12—C13—H13B | 108.6 |
N3—C4—C5 | 111.01 (17) | H13A—C13—H13B | 107.6 |
N3—C4—H4A | 109.4 | N15—C14—C19 | 121.31 (18) |
C5—C4—H4A | 109.4 | N15—C14—C13 | 117.71 (18) |
N3—C4—H4B | 109.4 | C19—C14—C13 | 120.98 (18) |
C5—C4—H4B | 109.4 | C14—N15—C16 | 117.85 (16) |
H4A—C4—H4B | 108.0 | C14—N15—Cu1 | 121.13 (13) |
C6—C5—C4 | 112.82 (17) | C16—N15—Cu1 | 117.60 (12) |
C6—C5—H5A | 109.0 | N15—C16—C17 | 123.75 (18) |
C4—C5—H5A | 109.0 | N15—C16—H16 | 118.1 |
C6—C5—H5B | 109.0 | C17—C16—H16 | 118.1 |
C4—C5—H5B | 109.0 | C16—C17—C18 | 118.20 (19) |
H5A—C5—H5B | 107.8 | C16—C17—H17 | 120.9 |
N7—C6—C11 | 120.95 (19) | C18—C17—H17 | 120.9 |
N7—C6—C5 | 117.30 (17) | C19—C18—C17 | 118.69 (19) |
C11—C6—C5 | 121.76 (18) | C19—C18—H18 | 120.7 |
C6—N7—C8 | 119.15 (17) | C17—C18—H18 | 120.7 |
C6—N7—Cu1 | 120.63 (13) | C18—C19—C14 | 120.17 (19) |
C8—N7—Cu1 | 119.12 (13) | C18—C19—H19 | 119.9 |
N7—C8—C9 | 122.55 (18) | C14—C19—H19 | 119.9 |
N7—C8—H8 | 118.7 | H22A—O22—H22B | 99 (3) |
C9—C8—H8 | 118.7 |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···Cl20 | 0.75 (2) | 2.51 (2) | 3.2379 (15) | 162 (3) |
N3—H3···Cl20 | 0.77 (3) | 2.57 (3) | 3.3132 (18) | 162 (3) |
O21—H21A···Cl20 | 0.73 (2) | 2.48 (2) | 3.190 (2) | 166 (3) |
O22—H22A···Cl20ii | 0.80 (2) | 2.45 (2) | 3.241 (2) | 175 (3) |
O22—H22B···Cl20 | 0.81 (2) | 2.40 (2) | 3.206 (2) | 176 (3) |
Symmetry code: (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(OH)2(C14H17N3)2]Cl2·6H2O |
Mr | 794.70 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 9.2875 (2), 9.9802 (2), 10.9261 (2) |
α, β, γ (°) | 63.4321 (8), 82.2565 (7), 77.9460 (8) |
V (Å3) | 884.85 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.41 |
Crystal size (mm) | 0.36 × 0.21 × 0.07 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.631, 0.908 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17493, 4033, 3781 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.088, 1.06 |
No. of reflections | 4033 |
No. of parameters | 228 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.71 |
Computer programs: COLLECT (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), local program.
Cu1—O2 | 1.9528 (13) | Cu1—N7 | 2.0175 (16) |
Cu1—O2i | 1.9527 (14) | Cu1—N15 | 2.2646 (16) |
Cu1—N3 | 2.0298 (16) | Cu1—Cu1i | 3.0194 (4) |
O2i—Cu1—O2 | 78.73 (6) | O2i—Cu1—N15 | 101.78 (6) |
O2i—Cu1—N7 | 91.06 (6) | O2—Cu1—N15 | 93.65 (6) |
O2—Cu1—N7 | 162.93 (6) | N7—Cu1—N15 | 101.88 (6) |
O2i—Cu1—N3 | 160.57 (7) | N3—Cu1—N15 | 95.24 (6) |
O2—Cu1—N3 | 91.00 (6) | Cu1i—O2—Cu1 | 101.27 (6) |
N7—Cu1—N3 | 94.57 (7) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···Cl20 | 0.75 (2) | 2.51 (2) | 3.2379 (15) | 162 (3) |
N3—H3···Cl20 | 0.77 (3) | 2.57 (3) | 3.3132 (18) | 162 (3) |
O21—H21A···Cl20 | 0.73 (2) | 2.48 (2) | 3.190 (2) | 166 (3) |
O22—H22A···Cl20ii | 0.80 (2) | 2.45 (2) | 3.241 (2) | 175 (3) |
O22—H22B···Cl20 | 0.81 (2) | 2.40 (2) | 3.206 (2) | 176 (3) |
Symmetry code: (ii) −x+1, −y, −z+1. |
O21···O21ii | 2.831 (4) |
O23A···O21iv | 2.869 (6) |
O23B···O21iv | 2.663 (9) |
O23C···O21iv | 2.881 (11) |
O23A···O22 | 2.803 (6) |
O23B···O22 | 2.706 (9) |
O23C···O22 | 2.766 (11) |
O23A···O23Biii | 2.862 (10) |
O23B···O23Ciii | 2.928 (15) |
We have recently reported an investigation of the coordination chemistry of bis[2-(2-pyridyl)ethyl]hydroxylamine and its conversion to bis[2-(2-pyridyl)ethyl]amine (bpea; Leaver et al., 2003). During the course of this work, we also crystallized the title compound, (I). Three other crystal structures are available of salts of related [Cu2(µ-OH)2(L)2]2+ complexes, where L is an N-alkylated bpea derivative (Karlin et al., 1984, 1990; Obias et al., 1998). One of these, however, has an unusual basal-apical pattern of [Cu2(µ-OH)2] bridging (Karlin et al., 1984), which is not structurally comparable with that in (I). \sch
The asymmetric unit of (I) contains half a formula unit, with the crystallographic inversion centre (1 − x, 1 − y, −z) lying at the centre of the [Cu2(µ-OH)2]2+ moiety. The five-coordinate Cu centre shows only small deviations from an ideal square-pyramidal geometry, with two basal OH− ligands and a bpea pyridyl donor at the apical site. The τ value calculated from the bond angles at Cu1 is 0.039 (2), which is very close to the ideal value of 0 for a square pyramid (Addison et al., 1984). The [Cu2(µ-OH)2]2+ unit forms a near-perfect diamond shape, with the two unique distances Cu1—O2 and Cu1—O2i being identical to within 3 s.u.s [symmetry code: (i) 1 − x, 1 − y, −z]. The Cu1—O2—Cu1i angle and Cu1···Cu1i distance are similar to those shown by the other two known [Cu2(µ-OH)2(LR)2]2+ complexes with basal-basal [Cu2(µ-OH)2] bridging, which lie in the ranges 98.4 (3)–100.9 (1)° and 3.012 (1)–3.119 (1) Å, respectively (Karlin et al., 1990; Obias et al., 1998). The Cl− anion Cl20 is hydrogen-bonded to the bpea N—H function and to the hydroxide O—H group. Atom Cl20 also accepts hydrogen bonds from three different water molecules (Table 2), yielding a distorted square-pyramidal coordination geometry at this atom [τ calculated from the H···Cl20···H angles is 0.26 (2)].
There are three unique water molecules in the lattice of (I). One of these, O22, is crystallographically ordered and forms hydrogen bonds to two different Cl− anions. Another one, water molecule O21, also has an ordered O atom. However, only one H atom attached to water molecule O21 could be located in the difference map, which also hydrogen bonds to atom Cl20. The second H atom is probably involved in a hydrogen bond to water molecule O21ii [Table 3; symmetry code: (ii) x, 1 − y, 1 − z]. In that case, the putative atom H21B must be disordered over at least two sites, being 50% occupied at a position lying near the O21···O21ii vector. This would explain our inability to locate this H atom. Finally, the third water molecule is disordered over three orientations, labelled O23A—O23C. Although the positions of the H atoms bonded to these partial O atoms could not be located, atoms O23A—O23C have several potential hydrogen-bonding partners lying 2.65–3.10 Å away (Table 3). There are also some short distances between O23A—O23Aiii [2.592 (12)], O23A—O23Ciii [2.511 (12)] and O23C—O23Ciii [2.60 (2) Å], which are substantially closer than the sum of the van der Waals radii of two O atoms (2.8 Å; Pauling, 1960) [symmetry code: (iii) 2 − x, −y, 1 − z]. This implies that when the O23A or O23C sites are occupied, only site O23Biii can be occupied in the neighbouring disordered region, but, when site O23B is occupied, either O23Aiii, O23Biii or O23Ciii can be present. However, the fractional occupancies for O21A:O21B:O21C predicted by this simple model (0.20:0.60:0.20) do not match those observed (0.40:0.35:0.25). Thus, there must be additional geometric or steric factors controlling the disorder of this water molecule, which cannot be elucidated in the absence of the partial H-atom positions attached to O21 and O23A—O23C. There are no other noteworthy intermolecular interactions in the crystal lattice.